KR20070057928A - Leather-like sheet material, process for producing leather-like sheet material, and ball using the same - Google Patents

Abstract

A sheet material having protrusions on its surface is provided. The sheet material includes a substrate layer formed of extrafine fibers and a polymeric elastomer (A). A composite layer formed of fuffed extrafine fibers continued from the fibers constituting the substrate layer and an polymeric elastomer (B) bonded to the extrafine fibers is provided on one surface of the substrate layer. Further, a covering layer composed mainly of a polymeric elastomer (C) is provided on the top of protrusions on the surface of the sheet material, and a through-hole extended from the surface side to the substrate layer is provided on the side part between the top of the protrusions and the valley bottom part of the protrusions. Further, preferably, the covering layer has a multilayer structure of two or more layers, and the surface side layer in the covering layer contains a pressure-sensitive adhesive. Preferably, the pressure-sensitive adhesive is a liquid rubber or a rosin resin, and the liquid rubber is a synthetic liquid rubber having a molecular weight of 800 to 5000.

Description

Leather-type sheet, manufacturing method of leather-like sheet and ball using the same {LEATHER-LIKE SHEET MATERIAL, PROCESS FOR PRODUCING LEATHER-LIKE SHEET MATERIAL, AND BALL USING THE SAME}

TECHNICAL FIELD The present invention relates to a leather-like sheet-like article, and more particularly, to a leather-like sheet-like article suitable for a ball game such as a basket, rugby, football, handball, a manufacturing method thereof, and a ball using the same.

As skin materials for ball balls, natural leather has been used for a long time, but recently, leather-like sheet-like articles, especially leather-like sheet-like articles made of fibers and polymer elastomers, have been widely used for ease of handling. However, in order to prevent abrasion resistance and adhesion of contaminants, the surface of artificial leather is often formed on one surface by a skin layer made of a polymer elastomer, and thus is easily slipped, and is often handled by a hand such as a basket, rugby, football, etc. In the case of sweating on the hands in the ball game, there is a problem that slip is likely to occur.

As a means for reducing such slippage and improving grip properties when wet, for example, Japanese Patent Application Laid-open No. Hei 9-250091 gives a non-slip resin exhibiting non-slipness to the surface of artificial leather having hair growth. A method is disclosed. However, this has a problem in that it is absorbable at the nap part, but the lint is present from the beginning, the durability and abrasion resistance are insufficient, and the film layer is not easily formed on the surface, thus causing contamination. In addition, there was a problem in that the surface of the napped portion was excessively absorbed and the ball became heavy.

Disclosure of the Invention

Problems to be Solved by the Invention

The object of the present invention is that the sheet-like article, which could not be achieved by these conventional sheet-like articles, is excellent in grip wetness and abrasion resistance at the same time as the wet sheet, and also absorbs excessive sweat and absorbs rainwater. It is an object to provide a leather-like sheet-like article, a method of manufacturing the same, and a ball using the same, which are particularly suitable for ball games such as baskets, rugby, football, and handball.

Means to solve the problem

The leather-like sheet-like article of the present invention is a sheet-like article having projections on its surface, and on the one side surface of the substrate layer made of the ultrafine fibers and the polymer elastic body (A), the microfibers having the shape of the hair continuous to the fibers constituting the substrate layer and The composite layer which consists of the polymer elastic body (B) joined to the ultrafine fiber exists, and the coating layer which mainly consists of the polymer elastic body (C) exists in the top part of the processus | protrusion of the sheet-like object, and is located in the side part between the top part of a processus | protrusion part, and a grain part It has a through hole which reaches a gas layer from the surface side, It is characterized by the above-mentioned. In addition, the fineness of the fine fibers is 0.0001 to 0.05 dtex, the composite layer is a two-layered multilayer structure, the gas layer side of the polymer elastomer (B) of each layer is a polymer elastomer (B1), and the coating layer is a polymer elastomer (B2). ), And the polymer elastic body (B2) is preferably a silicone-modified polyurethane.

Moreover, it is preferable that the coating layer has a multilayer structure of two or more layers, and the layer on the surface side of a coating layer contains an adhesive, Furthermore, an adhesive is liquid rubber or rosin resin, The liquid rubber is a synthetic liquid whose molecular weight is 800-5000. It is preferable that it is rubber.

It is preferable that the shape of the protrusion on the surface has an average area of 0.5 to 7 mm 2 at the top of the protrusion, the height difference between the top and the valley is 0.1 mm or more, and it is preferable that the through-holes of the side portions of the protrusion are 50 or more per one protrusion. .

Another manufacturing method of the leather-like sheet-like article of this invention consists of an ultrafine fiber and a polymeric elastic body (A), and apply | coats the solution which consists of a polymeric elastic body (B) to the sheet-like thing which has a microfine fiber hair on the one side surface. Then, a projection is formed on the surface of the sheet-like article by an embossing roll, and a solution mainly containing a polymer elastic body (C) is applied to the top of the projection.

Another ball of the present invention is characterized by adhering the leather-like sheet-like article of the present invention to the surface of the ball body.

To practice the invention  Best form for

The leather-like sheet-like article of the present invention is a sheet-like article having projections on its surface, and the base layer is composed of ultrafine fibers and a polymer elastic body (A). Moreover, it is also preferable to use together the fiber of normal fineness other than an ultrafine fiber, the scrim which consists of a woven fabric, etc. for the purpose of reinforcement to a base layer.

The ultrafine fibers constituting the base layer are preferably synthetic fibers, and particularly preferably polyester fibers such as polyamide fibers such as nylon 6, nylon 6,6, nylon 12, polyethylene terephthalate, and polybutylene terephthalate. . As fineness of these ultrafine fibers, it is preferable that they are 0.0001-0.05 dtex. When the fineness is large, the surface smoothness becomes difficult to be obtained, and the roughness of the cotton tends to lower the commodity value. In addition, when the fineness is too small, it is difficult to produce industrially stably.

Such ultrafine fibers, for example, create sea island-type composite spun fibers, mixed spun fibers or split composite spun fibers composed of two or more fiber-forming polymer polymers having different solvent solubility, and include cards, cross wrappers, From the entangled fiber nonwoven fabric which has undergone a process such as needle punching and hot pressing, one component can be extracted and removed by solvent extraction, or the composite fiber can be divided by physical or chemical means to form an ultrafine fiber. . For example, it is preferable to use the polyamide fiber or polyester fiber as the island component which becomes an ultrafine fiber, and to select a low density polyethylene, polystyrene, polypropylene, etc. as sea component.

At this time, examples of the polymer elastomer (A) used in the gas layer together with the ultrafine fibers include polyurethane elastomers, polyurethane urea elastomers, polyurea elastomers, polyester elastomers, synthetic rubbers, and the like. Among them, polyurethane elastomers are preferable. . Polyurethane elastomers include polyether-based diols such as polyethylene glycol and polytetramethylene ether glycol, ester-based diols such as polyethylene adipate and polybutylene adipate, polybutylene carbonate diol, polyhexamethylene carbonate diol and the like Polymer diols having a molecular weight of 800 to 4000, such as diols, diisocyanates such as tolylene diisocyanate, diphenylmethane 4,4 'diisocyanate, hexamethylene 1,6 diisocyanate, 3,3,5trimethyl 5 isocyanate and methylcyclohexyl isocyanate What reacted low molecular chain extenders, such as ethylene glycol, tetramethylene glycol, propylenediamine, 3,3,5 trimethyl 5 aminomethyl cyclohexylamine, can be used.

The gas layer of this invention impregnates the fibrous base material which consists of mixed spinning fiber or a composite spinning fiber before it became an ultrafine fiber, for example, the organic-solvent solution of a polymeric elastic body (A), or an aqueous emulsion, and then makes the fiber ultrafine Although it can obtain by making it etc., in order to make a protrusion part sharp, it is preferable that the polymeric elastic body (A) employs the wet-impregnation method using organic solvent solutions, such as DMF.

At this time, it is preferable that ratio (R / F) with respect to the weight (F) of the fiber which comprises the fibrous base material of the weight (R) of the polymeric elastic body (A) of a base layer is the range of 0.5-1.5, and further 0.6 As mentioned above, it is especially preferable that it is 0.65 or more. When this R / F value is large, the shape of the surface projections is sharp, and when this sheet-like article is used, there is a tendency that the shape change of the projections is small. It is preferable that it is an independent shape as a projection part, It is especially suitable for the retention of deep patterns, such as a conical trapezoidal emboss pattern, and can process the ball which is excellent in product quality. In order to improve R / F, it is necessary to increase the concentration of the polymer elastomer in the impregnation liquid, and the viscosity tends to increase, but it is obtained by employing a method of forcibly indenting a fibrous substrate in a plurality of rolls in the impregnation liquid. Can be.

In the sheet-like article of the present invention, it is essential that a composite layer made of a filament-like ultrafine fiber continuous to the fibers constituting the base layer and a polymer elastic body (B) bonded to the ultrafine fibers is present on one side surface of the base layer. Shall be. As the polymer elastic body (B), the same one as the polymer elastic body (A) described above can be used, but it is preferably a polycarbonate-based polyurethane. As solid content adhesion amount of a polymeric elastic body (B), it is preferable that it is the range of 5-30 g / m <2>. It is preferable that the fine-fiber of the filamentous shape is homogeneous, and that the same material as that of the known suede-like, nubuck-like artificial leather having no non-uniformity in the hair is used as the base material.

Moreover, it is preferable that this composite layer has a multilayer structure of two or more layers, and the gas-layer side of the polymeric elastic body (B) of each layer consists of a polymeric elastic body (B1), and a coating layer side consists of a polymeric elastic body (B2). The polymer elastic body (B1) on the gas layer side is preferably a polycarbonate-based polyurethane using an aliphatic, alicyclic, or aromatic isocyanate having a polycarbonate-based soft segment, and the 100% elongation modulus is 60 to 150. It is preferable that it is kg / cm <2> and 80-130 kg / cm <2> further. As solid content adhesion amount, it is preferable that it is the range of 1.5-5 g / m <2>.

The polymeric elastomer (B2) on the coating layer side is also preferably a polycarbonate-based polyurethane using an aliphatic, cycloaliphatic, or aromatic isocyanate having a polycarbonate-based soft segment, but also 5 to 30% by weight of the polyurethane weight, Moreover, it is preferable that it is the silicone modified polyurethane which introduce | transduced 10-20 weight% of silicone segments. In the case where the silicone-modified polyurethane is used here, the projections become clearer, the sharpness and the retention of the pattern are good, and a unique smooth feeling and feel can be obtained. As 100% elongation modulus of a polymeric elastomer (B2), it is preferable that it is 60-180 kg / cm <2>, Furthermore, it is 80-130 kg / cm <2>. As solid content adhesion amount, it is preferable that it is the range of 5-25 g / m <2>, and also the range of 10-20 g / m <2>.

In the sheet-like article of the present invention, a coating layer mainly composed of the polymer elastic body (C) exists at the top of the protrusion forming the protrusion of the surface, and at the side surface between the top of the protrusion and the bottom of the protrusion, the layer reaches the base layer. It is essential to have a through hole. Moreover, it is preferable that a coating layer has a multilayer structure of two or more layers, and the layer at the outermost surface side of a coating layer contains an adhesive, The adhesive is liquid rubber or rosin resin, and liquid rubber synthesizes molecular weight 800-5000. It is preferable that it is a liquid rubber. Although the coating layer which mainly uses a polymer elastic body (C) may exist in parts other than the top part of a processus | protrusion, when the through-hole which reaches a gas from a surface is not closed, it is preferable that it is not fundamentally.

As such a polymer elastic body (C), the same thing as the above-mentioned polymer elastic body (B) can be used, The single or 2 or more types of mixed diol and aliphatic of polycarbonate diol, polyetherdiol, and polyesterdiol of molecular weight 800-4000, It is preferable that it is a polyurethane elastomer using an alicyclic and aromatic isocyanate. Moreover, as 100% elongation modulus, it is preferable that it is 60-130 kg / cm <2>, Furthermore, it is 80-110 kg / cm <2>. When the 100% elongation stress is small, the grip property is improved but the wear resistance tends to be lowered. On the contrary, when the 100% elongation stress is large, the wear resistance is improved but the grip property tends to be lowered. As solid content adhesion amount of a polymeric elastic body (C), it is preferable that it is the range of 5-30 g / m <2>. Moreover, as thickness of a coating layer, it is preferable that it is 10-500 micrometers.

In addition, it is preferable that this polymer elastic body (C) also has a multilayer structure comprised from 2 or more types of polymer elastic bodies, In that case, the polymer elastic body (C) also has the same component as the polymer elastic bodies (B1) and (B2) of a composite layer. It is preferable that polymeric elastic bodies (C1) and (C2) exist from a side.

The polymer elastic body (C2) constituting the layer on the surface side of the coating layer may be a normal polyurethane elastomer, but is also a silicone-modified poly having introduced a silicone segment of 5 to 30% by weight and 10 to 20% by weight of the polyurethane. It is preferable that it is urethane, and it is especially preferable that it is a silicone-modified polycarbonate aliphatic or alicyclic non-yellowing polyurethane elastomer. When such silicone modified polyurethane is used here, abrasion resistance improves and a unique smooth feeling and a touch can be acquired.

Moreover, it is preferable to contain an adhesive in the layer of the outermost surface side of a coating layer. In this case, it is preferable that the polymeric elastic body (C1) consists of three or more layers of structures of the polymeric elastic body (C2 ') and the polymeric elastic body (C2') containing an adhesive from the base layer side. As the solids adhesion amount, the polymer elastic body (C1) is in the range of 1.5 to 5 g / m 2 from the gas layer side, and the polymer elastic body (C2) is in the range of 2 to 8 g / m 2 or greater than or equal to (C1), and contains an adhesive. It is preferable that a polymeric elastic body (C2 ') exists in the range of 4-20 g / m <2>.

Examples of the pressure-sensitive adhesive preferably contained in the polymer elastic body (C) of the layer on the outermost surface side include rosin resins, liquid rubbers, and the like, and can be used alone or in combination. Among them, low molecular weight synthetic rubber having a molecular weight of 1000 to 4000, which is a liquid rubber, is preferable, and low molecular weight polybutadiene, low molecular weight acrylonitrile butadiene copolymer, low molecular weight polydicyclopentadiene and the like are particularly preferable. Moreover, it is preferable that content of the adhesive in a surface layer is 5-100 weight part with respect to 100 weight part of polymer elastic bodies, Furthermore, it is 10 parts-85 parts, Most preferably, they are 20 parts-70 parts. Although the addition amount needs to determine the optimum amount by the level of touch and grip coatability required, when the addition amount is too large, there is a tendency to cause a decrease in strength of the coating layer, a lack of wear resistance, and the like. Moreover, it is also preferable to blend gloss regulators, coloring pigments, and stabilizers, such as a silica, in this layer on the outer skin side, and the texture of surfaces, such as glossiness, can be adjusted.

Although the sheet-like object of this invention has a protrusion on the surface, it is preferable that the average area of the top part of a processus | protrusion part is 0.5-7 mm <2>, and the height difference of the top part of a processus | protrusion part and the valley part is 0.1 mm or more. Moreover, it is preferable that the through-hole of the side part of a projection part is 50 or more per one projection part.

Such a projection is particularly effective when used for American football or handball, in which the ball is held and handled by hand. Moreover, it is preferable that the total area of the top part of the processus | protrusion part exists in the ratio of 20 to 70% of a sheet area, and it is most preferable that the height difference is 0.15-1.2 mm especially 0.2-1.0 mm. Here, the area of a sheet-like object refers to the projected area seen from the surface side of the area of the sheet-like object itself, and differs from the surface area in consideration of the curved shape of the protrusion on the surface. Here, when the projection is observed from the side surface of the skin material, the top portion of the top of the projection portion and the distance between the grains is the top portion. By having a protrusion in this way, it is achieved by the dimension of high grip property and durability.

The protrusion may have a shape that is partially contiguous with the protrusion adjacent to the top, but it is more preferable that the protrusion is independent in order to increase the grip property. It is preferable that it is 0.5-7 mm <2>, and, as an average area of each top part of an independent projection part, it is preferable that it is 1.5-4.0 mm <2>. Moreover, as the number, it is preferable that it is about 5-100 pieces per 1 cm <2>. Moreover, it is preferable that it is 10-60 piece / cm <2>.

It is preferable that the shape of the independent protrusions is particularly conical trapezoidal in terms of durability, and the size of the diameter of the top of the cone trapezoidal protrusions is 0.8 to 30 mm, preferably 1.2 to 2.5 mm.

The sheet-like article of the present invention is required to have a through hole reaching the gas layer from the surface side at the side portion between the top of the protrusion and the valley, but there are also 50 or more, especially 100 or more through holes per projection. It is preferable. Moreover, it is preferable that it is 1000 or less from a viewpoint of pollution prevention property. Moreover, it is preferable that the number of the hole of the shoulder part near a top part among the side parts is large.

Moreover, it is preferable that the diameter of a hole is 0.5-300 micrometers, Furthermore, it is preferable that it is 1-200 micrometers, especially 100 micrometers or less. In the sheet-like article of the present invention having such a protrusion, a large number of holes exist in the side surface portion, whereby the grip property at the time of wetting can be improved without reducing the durability.

Here, the top of the protrusions, the protrusions of the protrusions, and the side portions therebetween, when the protrusions are observed from the side of the skin material, the tops of the protrusions and the elevations of the heights of the protrusions of the protrusions of the protrusions are higher than 1/10 from the top of the protrusions. A portion lower than 10, i.e., 2/10 from the grain, is the grain portion, and 1/10 to 8/10 from the top between them is the side portion.

Moreover, in the ball | skin skin material which has the protrusion part of this invention, it is preferable that openings exist also in the curved part of protrusion parts other than a side part part.

In the leather-like sheet-like article of the present invention, when such openings exist, the water film on the surface thereof is absorbed at the time of wetness, the grip property at the time of wetness can be improved, and the ball is created and used by suppressing excessive absorption. The weight increase of can be suppressed effectively. As absorption time of the sheet-like thing of this invention, it is preferable that it is 240 second or more, and it is preferable that it is the range of 300-600 second.

Such a leather-like sheet-like article of the present invention can be obtained, for example, according to the method for producing a leather-like sheet-like article as follows. That is, the solution which consists of a polymeric elastic body (B) is apply | coated to the sheet-like thing which consists of an ultrafine fiber and a polymeric elastic body (A), and has the microfiber filament on the one side surface, and forms a protrusion on the sheet-shaped object surface in an embossing roll. This is a method of applying a solution mainly composed of the polymer elastic body (C) to the top of the protrusion.

As a sheet-like article which has the ultrafine fiber hair on the one side surface used for the manufacturing method of this invention, the artificial leather normally called a suede wind can be used. This sheet-like article is composed of a fibrous aggregate using a mixed fiber or a composite fiber of a fine-fiber-island or split type and a polymer elastic body, and the fine-fiber hairs on one side of the sheet-like article are composed of ultra-fine fibers and a polymeric elastomer. It can obtain by grinding the surface of with sand paper etc. More specifically, by dissolving and removing the sea component of the fibrous base impregnated with a polyurethane resin in a nonwoven fabric made of mixed spun fiber of island-in-sea type, the fiber is microfiberized to obtain a sheet-like material, and the surface of the nonwoven fabric is mixed with the solvent of the polymer elastomer. It is preferable to fix it by gravure treatment, etc., and to grind the surface, and to obtain an ultrafine fiber hair. For example, when the polymer elastomer is a dimethylformamide (hereinafter referred to as DMF) soluble polyurethane for wet molding, DMF is applied and dried with 80 to 320 mesh gravure rolls, and the source of the ultrafine fibers is fixed. It is preferable to grind with a grinder equipped with sandpaper of 640 mesh.

Here, it is preferable that this ultrafine fiber hair is a uniform hair whose length is 0.01-0.2 mm, Preferably it is 0.1 mm or less, Especially preferably, it is 0.08 mm or less. Such hair growth can be obtained by a method for fixing an ultrafine fiber on the surface of a sheet made of an ultrafine fiber and a polymer elastic body, polishing conditions, or the like.

Next, as a manufacturing method of this invention, it is essential to apply | coat the solution which consists of a polymeric elastic body (B) to the sheet-like thing which has the ultrafine fiber hair on the one side surface. The polymer elastic body (B) is the same as the polymer elastic body (B) described above, but the solution for this undercoat is suitably in the range of 8 to 15% by weight and a viscosity of 100 to 200 cps.

Moreover, it is preferable that the composite layer which consists of an ultrafine fiber and a polymeric elastic body (B) is the multilayer structure of the above-mentioned polymeric elastic body (B1) and polymeric elastic body (B2) in application | coating of this polymeric elastic body (B). For that purpose, after apply | coating the solution which consists of a polymeric elastic body (B1), it is preferable to apply | coat the solution which consists of a polymeric elastic body (B2) again. At this time, it is preferable that the solution which consists of a polymeric elastic body (B1) is 8 to 12 weight% of a density | concentration, and viscosity is 100 to 180 cps, and it is preferable that it is a range of 20-50 g / m <2> and 25-35 g / m <2> as an application quantity. For example, it can obtain by gravure coating 1-2 rolls with the 50-80 mesh gravure roll to the sheet-like thing which has a microfiber filament. Moreover, it is preferable that the solution which consists of a polymeric elastic body (B2) is 8-15 weight% in concentration, and the viscosity is 100-250 cps, and it is preferable that it is the range of 100-180g / m <2> or more 160g / m <2> or less as application amount. After application | coating and drying of a polymeric elastic body (B1), it can obtain by gravure coating of 2-8 rolls, More preferably, 4-6 rolls with a 70-150 mesh gravure roll.

And in the manufacturing method of the leather-like sheet-like object of this invention, after apply | coating the solution which consists of a polymeric elastic body (B), a protrusion is formed in the surface of a sheet-like object with an embossing roll. As a pattern formed by the surface shape of a projection part, it is preferable to have a conical trapezoid shape projection part especially for a basket ball and a football. Thus, in order to provide the embossing pattern which has a projection part, it can carry out by pressing a sheet-like thing between embossing roll and a backing roll using the embossing roll which carved the inscription opposite to the surface pattern of the target sheet shaped object. have. Moreover, as the height difference of a metal mold | die protrusion, it is preferable that it is 0.2-1.5 mm, Most preferably, it is 0.3-1.0 mm.

By embossing in the metal mold | die which has a protrusion part of 0.1 mm or more, the side part used as the inclined surface of this protrusion part increases, and a hole can be drilled in the surface of the skin layer. A large shear force is applied to the sheet-like article along with heat from the top to the side of the projection, and through-holes that reach the gas layer from the surface side are generated on the sheet-like article surface. Moreover, it is preferable that the metal mold | die consists of the recessed part independent from the continuous process part of which part was continuous, and it is preferable that it is a female mold opposite to a conical trapezoidal processus | protrusion part. The size of the top of the projection of the sheet-like article can be performed by adjusting the shape of the mold, and the height of the projection can be performed by adjusting the depth of the mold and the pressure, temperature, and time during embossing.

Moreover, it is preferable that the conditions of the embossing are the softening temperature of -40 degreeC-+20 degreeC of the polymeric elastic body of a coat layer, and it is more preferable to press a sheet-like thing in the temperature range of -20 degreeC-+10 degreeC. For example, when the silicone-modified polycarbonate-based alicyclic non-yellowing polyurethane having a softening temperature of 180 ° C is used as the polymer elastomer (B), the embossing roll surface temperature is preferably in the range of 140 to 200 ° C, particularly around 180 ° C. This is optimal.

In the manufacturing method of this invention, the solution which mainly uses a polymeric elastic body (C) is apply | coated to the top part of the processus | protrusion part which generate | occur | produced by the embossing of a sheet-like thing. The polymer elastic body (C) is the same as the polymer elastic body (C) described above, but the solution for this phase coat is suitably in the range of 8 to 13% by weight and viscosity of 100 to 180 cps. The layer mainly composed of the polymer elastic body (C) can ensure the wear resistance of the surface layer of the protrusion, prevent adhesion of contaminants, suppress excessive absorbency, improve the feel (provide a smooth feeling), and the like. In addition, when the color of the top part of the projection part is changed by this application | coating using a pigment etc., the contrast of the color tone with the layer which consists of the polymeric elastic body (B) of a lower part can be provided, and therefore, the quality as a ball can be raised.

In addition, it is preferable that the application | coating of this polymeric elastic body (C) becomes a multilayer structure in which the coating layer by this top layer is two or more layers, and after apply | coating the solution which consists of the above-mentioned polymeric elastic body (C1), the same amount or more amount of polymer It is preferable to apply the solution which consists of elastic bodies (C2). Moreover, it is preferable to mainly apply a polymer elastic body (C2 ') to an outermost layer, and to apply the solution containing an adhesive. At this time, it is preferable that the solution which consists of a polymeric elastic body (C1) (C2) apply | coated first is a density | concentration 8-13 weight%, a viscosity 100-180 cps, and it is preferable that it is the range of 20-40 g / m <2> as an application quantity. For example, it can obtain by gravure coating for 1-4 rolls each with 70-110 mesh gravure roll in the top part of the projection part of a sheet form. It is preferable that the solution containing an adhesive mainly using the polymeric elastic body (C2 ') apply | coated after that is a density | concentration of 8-13 weight% and a viscosity of 100-180 cps, and it is preferable that it is a range of 20-80 g / m <2> as an application quantity. For example, it can obtain by gravure coating for 2-6 rolls with the gravure roll to the top part of the processus | protrusion part of a sheet form.

Moreover, when apply | coating the coating layer which consists of a polymeric elastic body to the top part of the processus | protrusion part of this invention, it is necessary to apply | coat so that the through-hole formed in the processus part side parts, such as a trapezoidal trapezoid, will not be blocked. In the case of the sheet-like article used in the present invention in which a large protrusion is generated on the surface, the openings on the side face are hardly blocked compared to the top portion and the curved portion, but the gravure coating is applied with a clearance of 70 to 98% of the sheet thickness. It is desirable to take the way. By applying the polymer elastic body only to the top of the projection, surface abrasion resistance is improved, and contaminants are hardly adhered to the skin material.

And another this invention is a ball which adhere | attached the leather type sheet-like thing obtained in this way to the ball | bowl body. As such, the leather-like sheet-like article can be formed into a ball for ball by applying pressure air to the inflated body, and is preferably used for basket balls, rugby balls, football balls, hand balls, and the like.

Hereinafter, the present invention will be described in detail by way of examples. In addition, this invention is not restrict | limited to the range of an Example, Unless specifically limited, a part or% shows a weight part and weight%. The measurement item of this invention is measured by the following.

(1) elongation stress

The film of thickness 0.1mm of JISK6301 No.2 type dumbbell test piece was made into the sample, and it measured on the conditions of 100% / min of extension | stretch rate by the constant-speed extension tester.

(2) dry friction coefficient

A skin material having a protrusion (width 2.5 cm, length 5 cm) on the surface of which temperature was adjusted for 24 hours at a temperature of 23 ° C. and a relative humidity of 60% was brought into contact with a stainless steel smooth plate, and a load of 500 g was applied. The frictional force (F) at the time of moving at a speed of 2 m / min was measured, and the dry friction coefficient μd = F / 500 was obtained. In addition, the frictional force F is an average value at the time of moving a test piece.

(3) wet friction coefficient

After immersing the test piece of the skin material (width 2.5cm, length 5cm) which has a protrusion on the surface for 24 hours in 23 degreeC water, the surface adhesion water is wiped off with tissue paper, and the surface is made to contact a stainless steel smooth plate, The load was applied, and the frictional force (F) (unit; g) at the time of moving at a speed of 2 m / min was measured, and the wet friction coefficient μw = F / 500 was determined. In addition, the frictional force F is an average value at the time of moving a test piece.

(4) wear resistance

It is measured according to JIS L1O79 6.15.3 C method (taber wear test). The wear wheel was equipped with 280 mesh sand paper, weight was 500 g, and the surface damage state of the test piece after abrasion 100 times was evaluated by the following rank.

Level 5: Less change in color and inconspicuous

Class 4: There is no problem in appearance only by damage of the surface coating layer.

Class 3: A portion of the porous coat layer is damaged (actually acceptable).

Class 2: The porous coat layer was significantly damaged, and the fibers of some substrate layers were exposed.

1st grade: The base material layer is also damaged considerably, and the fiber etc. are exposed.

(5) Number of holes and size of the top part of the projection part, the bend part and the side part part

The top of the protrusions, the protrusions of the protrusions, and the side portions therebetween present on the surface of the skin material are the tops of the tops of the protrusions and the elevation of the valleys of the protrusions when the protrusions are observed from the side of the skin material. For example, the portion of 8/10 or less from the top, that is, the portion 2/10 from the grain, is the grain portion, and the portion 1/10 to 8/10 from the top between them is the side portion.

In the Example, as described below, the number of holes and the size in each of the projections were measured, and the average value was multiplied by the number of the projections per cm 2 to calculate.

The number of holes and the size of the top of the projection is 200 times photographed by a scanning electron microscope, and the number of holes and the size of 0.5 to 50 μm is measured by measuring the number of holes and the size of the top of the five different projections. Marked.

The number of holes and the size of the valleys is 200 times photographed with a scanning microscope focusing on the corners of the skin material, the number of holes and the size of the holes are measured, and the number of holes of 0.5 to 50 µm and the average value thereof are obtained. It converted into sugar and displayed. Moreover, when it had an independent stone base, it measured around the different 5 protrusion part, and averaged it.

The measurement of the number of holes and the size of the side portions is performed by cutting the protrusions into four equal parts or more vertically and preventing the blurring of the focus because the side faces become the side faces of the three-dimensional protrusions, and scanning the side surfaces of the respective protrusion parts. The photograph taken 200 times by the electron microscope was used. For the five different projections, the number of holes and the size of the holes were measured, and the number of holes and the average value of 0.5 to 50 µm were obtained and displayed.

(6) hair length of gas layer

The napped surface of the surface was polished and polished and photographed at a magnification of 200 times with a scanning electron microscope, the length of the napped surface was measured for ten pieces, and the average length was determined.

(7) sharpness of emboss

The embossed leather pattern sheet embossed 30 cm square sample embossed pattern and the embossed roll pattern were compared and evaluated.

Class 5: The pattern is beautifully reproduced, and the quality is high.

Level 4: Reproducibility is good but quality is poor.

Class 3: practically acceptable range.

Level 2: Insufficient pattern reproducibility.

Level 1: Reproducibility of the pattern is poor.

(8) maintainability of emboss

The basket ball created using the leather-like sheet-like object was used for the game of 10 games, and the embossed pattern state was evaluated in 5 steps after that. Grade 5 is very good, grade 3 is a practical acceptable range, and grade 1 is poor.

(9) difficulty of contamination

The basket ball created using the leather-like sheet-like object was used for the game of 10 games, and the contamination state of the ball was evaluated after that by following.

Grade 5: No pollution and good

4th grade: a little color difference, but no problem.

Class 3: Contamination, but practically acceptable.

2nd level: Slightly large pollution.

Grade 1: There is a lot of pollution and is hard to remove even if I wipe it.

(10) grip feel, feel

The basket ball created using the leather-like sheet-like article was made into the dry state and the wet state wetted with water, and the athlete evaluated grip property and evaluated in 5 steps. Grade 5 is very good, grade 3 is a practical acceptable range, and grade 1 is poor.

(11) absorption time

A drop (0.02 cm 3) was added dropwise to the top of the projection part of the leather-like sheet-like article by using a burette at a distance of 10 mm in height, and the time from immediately after dropping to absorption was measured.

Example 1

(Gaseous layer composed of ultrafine fibers and polymer elastomer)

Nylon-6 and low density polyethylene were mixed at 50/50, melted and mixed in an extruder, mixed spinning at 290 ° C. to draw, oil-treated and cut to obtain 4.5 dtex and 51 mm short fibers. This was obtained through a card, cross wrapper, needle locker, and calendar process to obtain a nonwoven fabric of a fused fiber base material having a weight of 480 g / m 2, a thickness of 1.6 mm, and an appearance density of 0.3 g / cm 3.

On the other hand, as the polymer elastic body (A) for impregnation, mixed diol with a polytetramethylene ether glycol having a molecular weight of 2020, a polyhexamethylene carbonate diol having a molecular weight of 1980, diphenyl methane 4,4 'diisocyanate and ethylene glycol were used as dimethylformamide. Polyurethane elastomer (solid content 20%) of 100% elongation stress reacted as a solvent, 60 kg / cm <2> and heat-softening temperature 180 degreeC was created.

100 parts of this polyurethane elastomer solution, a porous regulator (polyoxyethylene-modified silicone: 0.5 parts of FG-10 Matsumoto Oils & Chemicals Co., Ltd. manufacture), 0.5 parts of low molecular weight cellulose propionate, 0.5 parts of brown pigment, a polymer elastomer for impregnation of the base material It was set as the solution (impregnation liquid).

Subsequently, the fibrous substrate was immersed in the impregnation solution, and the nip roll was repeatedly passed through to sufficiently replace the impregnation liquid and the air in the substrate, and then squeezed at 96% of the substrate thickness to give 10% of DMF (dimethylformamide). It solidified in the 20 degreeC solidified water to contain, and washed with water and dried. The obtained sheet was repeatedly compressed and relaxed in hot toluene at 90 ° C to extract polyethylene which is a sea component in the mixed spun fiber, and then this was immersed in hot water at 95 ° C and azeotropically removed.

This is a fibrous substrate made of ultrafine fibers with an average fineness of 0.003 dtex. The weight ratio of nylon-6 fibers (F): impregnated resin (R) is 45:55, and the resin content ratio (R / F) to fiber weight is 1.22. The thing with a high resin filling rate with respect to a fiber component was obtained.

(Leather type seat shape product)

About 35 g / m <2> of DMF was apply | coated to the surface of the obtained base material with 200 and 180 mesh gravure roll. Then, a pulverized sheet-like article having an ultrafine fiber hair having a mean fineness of 0.003 dtex and a hair length of 0.06 mm was buffed with a polishing machine equipped with 600 mesh sand paper.

Next, the following coating liquid was created as a solution for undercoat resin (1) containing a polymeric elastic body (B1).

Resin for sewerage (1)

Polycarbonate alicyclic yellowing-free polyurethane (100% elongation stress 130kg / cm 2, solid content 20%). 100 copies

Mixed solvent (MEK: IPA: DMF = 5: 4: 1): 100 parts

Color Pigment (Brown): 0.6 part

Next, the following coating liquid was created as a solution for undercoat resin (2) containing a polymeric elastic body (B2).

Resin for sewerage (2)

Silicone modified polycarbonate alicyclic yellowing-free polyurethane (100% elongation stress 65㎏ / ㎠, solid content 20%): 100 parts

Mixed solvent (MEK: IPA: DMF = 5: 4: 1): 100 parts

Color Pigment (Brown): 0.6 part

The undercoat resin (1) was apply | coated 35g / m <2> by 70 mesh roll and 1 roll, and the undercoat resin (2) was apply | coated 130g / m <2> in total with 3 rolls of 70 mesh and 1 roll of 110 mesh.

Subsequently, the surface of the sheet-like article after the completion of the undercoating was treated at an roll surface temperature of 180 ° C., a pressure of 350 kg / m, and a processing speed of 1.5 m / min using an embossing machine equipped with an emboss roll in which steam was sealed. And the sheet-like object which has independent protrusion part was obtained. As the embossing roll, it has 24 concave-shaped independent depressions of conical trapezoidal shape, the maximum diameter of the top part of the projection part after transferring is 1.8 mm, the maximum diameter of the bottom part of the projection part is 2.3 mm, and the height of the conical trapezoid is 0.6 mm. The roll which can be heated with the fruit-shaped metal mold | die of the shape of was created and used.

The sheet-like article after embossing had a conical trapezoidal protrusion, and an average of 500 holes per hole of 1 to 200 µm existed on the side surface of the protrusion. Moreover, the opening showed much distribution in the shoulder part of the side of the projection part. There was no through hole at the top of the protrusion.

Then, in order to give the quality and design of a ball | bowl to the top of embossing, the coating material which has the color and contrast of the embossed curved part was apply | coated.

At this time, the resin to be used for the top coat (1) as the polymer elastic body (C) was a polycarbonate alicyclic non-yellowing polyurethane (100% elongation stress 130 kg / cm 2, solid content 20%) used in the undercoat (1). As the top coat (1), the coating liquid of the resin concentration of 11% which added the dark brown pigment to the coloring pigment of the undercoat (1) was apply | coated once with 110 gravure roll so that it might become 25 g / m <2> per WET unit area. . Then, 40 g / m <2> of 13% solutions of the silicone-modified carbonate-type yellowing-free polyurethane elastomer used for the undercoat (2) as the topcoat (2) were apply | coated.

Next, in order to finish on the surface satisfying the main characteristics such as touch, grip feel, fragility, and wear resistance as a ball, a top coat 3 containing a grip skin enhancer was prepared, and applied three times with 70 mesh gravure rolls. It applied 60 g / m <2> in film shape, and dried.

Topcoat (3)

Silicone-modified polycarbonate-free yellowing polyurethane resin (100% elongation stress 65㎏ / ㎠, solid content 20%): 100 parts

Low molecular weight polybutadiene (molecular weight 2000): 15 parts

Silica: 0.3 parts

Mixed solvent (MEK: IPA: DMF = 5: 4: 1): 343 parts

The obtained leather-like sheet-like object was sufficiently excellent in the grip property at the time of wetness, since absorption time was suitable for 300 second. The leather-like sheet-like object was processed and evaluated by American football ball, and as a result, even in the state of attachment of sweat, the slippage was good, grip grip property was not excessively absorbed, the weight increase of the ball during the game was small, and the wear resistance was also not a problem.

The base material characteristics of the obtained leather-like sheet-like thing were shown in Table 1, Table 2.

Example 2

A leather-like sheet-like product was produced in the same manner as in Example 1, except that the impregnation liquid for the base material of Example 1 was diluted with DMF. R / F (resin / fiber ratio) of the obtained base material layer was 0.66 with respect to 1.22 of Example 1. Although the obtained sheet had some difference in the sharpness of embossing compared with the thing of Example 1, it was excellent in abrasion resistance, feel, and grip property without a problem practically as a ball material. The base material characteristics of the obtained leather-like sheet-like thing were shown in Table 1 and Table 2 together.

Example 3

Instead of the mixed spun fiber used in Example 1, nylon-6 / low density polyethylene was mixed at 50/50, melted in an extruder, and the spinning time was shortened to 1/3 of Example 1 in the pack. The average fineness of nylon-6 of the island component of the obtained mixed spun fiber was 0.0005 dtex. The processing similar to Example 1 was performed using this fiber. The obtained leather-like sheet-like article had the quality of the surface as a ball material, and was abundant in abrasion resistance and grip property. The base material characteristics of the obtained leather-like sheet-like thing were shown in Table 1 and Table 2 together.

Example 4

70 mesh and 2 rolls were added to the undercoat resin 2 of Example 1, the application amount of the undercoat resin 2 was increased from 13 g / m <2> to 18 g / m <2> by solid content, and other conditions were based on Example 1. Was carried out. The obtained sheet was rich in surface smoothness, had good abrasion resistance, and had no excessive absorption rate, thereby satisfying the required characteristics. The base material characteristics of the obtained leather-like sheet-like thing were shown in Table 1 and Table 2 together.

Example 5

As the impregnation solution, polyhexamethylene carbonate diol having a molecular weight of 2000, diphenylmethane 4,4 'diisocyanate and ethylene glycol were reacted with dimethylformamide as a solvent, and a polyurethane elastomer (solid content concentration 30%, 100% elongation stress 80 kg / cm 2) And thermal softening temperature 185 ° C) were obtained.

The obtained polyurethane elastomer was diluted with DMF to prepare an impregnation liquid containing 22% polyurethane, and the mixed spinning fiber nonwoven fabric used in Example 1 was immersed in this impregnation liquid, and the nip and relaxation were repeated five times with a metal roll. Similarly to Example 1, this was immersed in hot toluene at 95 ° C., compressed and relaxed by a stainless steel nip roll stamped on the surface, and polyethylene was extracted and removed, which was then azeotropically removed in 100 ° C. hot water. This sheet was filled with 1.4 times the impregnation resin with respect to the fiber weight.

Using this sheet, processing was performed in the same manner as in Example, and processed into a leather-like sheet. The obtained leather-like sheet-like article for ball disk is absorbed in spite of the sharpness of the embossed pattern and the retention of the pattern when the practical test is repeated after processing with the ball, and excellent in touch and grip properties. The change in weight during play was also small and was particularly excellent as a skin material for American football balls and basket balls. The base material characteristics of the obtained leather-like sheet-like thing were shown in Table 1 and Table 2 together.

Comparative Example 1

Instead of the mixed spun fiber used in Example 1, a composite fiber having a sea component of polyethylene (fineness 4.5 dtex, length 51 mm) in which 19 dextrose nylon-6 fibers were present in one of the parent yarns was prepared. Other conditions were based on Example 1, and created the sheet-like thing. The results are shown in Table 1. The obtained sheet-like article could not settle the fluff of the surface of the napped fiber by the undercoat coating liquid, but after processing, it became the roughness, and lacked the quality even after making it into a ball. The base material characteristics of the obtained leather-like sheet form were shown in Table 3 and Table 4.

 Comparative Example 2

An impregnating base material and a leather-like sheet were prepared in accordance with the conditions of Example 1 except that the concentration of the impregnation liquid used in Example 1 was 14% (20% polyurethane elastomer; 100 parts, DMF; 42.9 parts). Created. The obtained base material had a resin ratio with respect to a fiber as low as 0.26, lacked the sharpness of the embossed pattern of the final sheet-like thing, the deformation | transformation of the pattern in use process was large, and the quality fell as a ball material. The base material characteristics of the obtained leather-like sheet form were shown in Table 3 and Table 4 together.

Comparative Example 3

After the embossing for the basket ball was applied to the napped sheet obtained by buffing in Example 1 without applying the bottom coat resin, a finishing resin containing a gripper improving agent was applied to a 40 mesh gravure engraving roll without applying top coat resin. Was applied twice. This was easy to be contaminated without forming a resin film on the napped surface and insufficient wear resistance. The base material characteristics of the obtained leather-like sheet form were shown in Table 3 and Table 4 together. [Comparative Example 4]

After impregnating the impregnated resin into the nonwoven fabric made of the mixed spun fiber obtained in Example 1, a 15% solution of a polyurethane elastomer having the same composition as the impregnated resin was recoated onto the surface of the substrate and subjected to wet coagulation, and the surface of the polyurethane wet porous A sheet with a layer was obtained.

This sheet was pressed at a surface temperature of 160 ° C with a basket-shaped embossing roll to obtain a sheet having independent protrusions.

The sheet after embossing had a conical trapezoidal protrusion, and an average of 2000 holes per 1 protrusion were present on the side surface of the protrusion.

Next, 100 parts of polyurethane elastomers having the same polyurethane resin composition as the porous layer, 200 parts of a mixed solvent having MEK: IPA: DMF = 5: 4: 1 and 1 part of a brown pigment were mixed to prepare a coating liquid having a concentration of 10.3% and a viscosity of 140 cps. It applied to the top part to the disk of the embossed embossing which was created first.

343 parts of the same mixed solvent, 0.6 parts of a secondary pigment, 0.6 parts of polybutadiene of molecular weight 2000, and 0.3 parts of silica were mixed and dissolved again in 100 parts of coating resin, and the coating liquid for coating layers containing an adhesive was apply | coated.

The obtained leather-like sheet had good abrasion resistance, grip skin resistance, and the like, but the touch was not sufficient. The base material characteristics of the obtained leather-like sheet form were shown in Table 3 and Table 4 together.

Advantageous Effects of Invention According to the present invention, in addition to drying, wet grip and wear resistance are also excellent, and the weight change of the sheet-like product due to excessive absorption of sweat and rainwater is particularly small, such as a basket, rugby, football, handball, etc. A leather-like sheet-like article suitable for the ball game ball of the present invention, a production method thereof, and a ball using the same are provided.

Claims (26)

A sheet-like article having projections on its surface, wherein the one-sided surface of the base layer composed of the ultrafine fibers and the polymer elastomer (A) is a filament-like ultrafine fiber continuous to the fibers constituting the base layer and a polymer elastic body bonded to the ultrafine fibers ( The composite layer which consists of B) exists, and the coating layer which mainly consists of a polymer elastic body (C) exists in the top part of the processus | protrusion part of the sheet-like object, and the side part between a processus top part and the processus | protrusion part curvature reaches a gas layer from the surface side. Leather-like sheet-like article having a through hole. The method of claim 1, Leather-like sheet material with fineness of 0.0001 to 0.05dtex. The method of claim 1, The leather-like sheet-like object whose ratio (R / F) with respect to the weight (F) of the fiber which comprises the nonwoven fabric of the weight (R) of the polymeric elastic body (A) of a base layer is 0.5-1.5. The method of claim 1, A leather-like sheet-like article in which the ultrafine fibers in the gas layer are in the form of microfine fiber bundles. The method of claim 1, A leather-like sheet material in which the polymer elastic body (A) in the base layer is porous. The method of claim 1, Leather-like sheet material having a thickness of the coating layer 10 ~ 150㎛. The method of claim 1, A composite sheet is a multilayer structure having two or more layers, wherein the gas layer side of the polymer elastic body (B) of each layer is made of a polymer elastic body (B1) and the coating layer side is made of a polymer elastic body (B2). The method of claim 7, wherein A leather-like sheet-like article wherein the polymer elastomer (B2) is a silicone-modified polyurethane. The method of claim 1, The leather-like sheet-like thing whose coating layer is a multilayer structure of two or more layers, and the layer of the surface side of a coating layer contains an adhesive. The method of claim 9, The leather-like sheet-like article whose adhesive is liquid rubber or rosin resin. The method of claim 10, The leather-like sheet-like thing whose liquid rubber is synthetic liquid rubber whose molecular weight is 800-5000. The method of claim 1, The leather-like sheet-like object whose average area of a top part of a processus | protrusion part is 0.5-7 mm <2>, and the height difference of a protrusion top part and a valley part is 0.1 mm or more. The method of claim 1, Leather-like sheet-like material having at least 50 through-holes per side projection. A solution composed of the polymer elastic body (B) is applied to a sheet-like material composed of ultra-fine fibers and a polymer elastic body (A) and having an ultra-fine fiber hair on one side surface thereof, and a protrusion is formed on the surface of the sheet-shaped object with an embossing roll. A method for producing a leather-like sheet-like article comprising applying a solution mainly containing a polymer elastomer (C) to the top. The method of claim 14, The manufacturing method of the leather-like sheet-like thing whose height difference of the top part of a projection part and the bend part is 0.1 mm or more. The method of claim 14, The manufacturing method of the leather-like sheet-like thing whose average area of a protrusion top part is 0.5-7 mm <2>. The method of claim 14, The manufacturing method of the leather-like sheet-like thing whose fineness of an ultrafine fiber is 0.0001-0.05 dtex. The method of claim 14, The manufacturing method of the leather-like sheet-like thing whose ratio (R / F) with respect to the weight (F) of the ultrafine fiber of the weight (R) of the polymeric elastic body (A) in a sheet-like thing is the range of 0.5-1.5. The method of claim 14, A method for producing a leather-like sheet-like article in which the sheet-like article is impregnated with a polymer elastic body (A) in a structure composed of ultrafine fiber-forming fibers, and then microfiberized. The method of claim 14, The method for producing a leather-like sheet-like article wherein the sheet-like article is wet-coagulated after impregnating the polymer elastomer (A). The method of claim 14, The manufacturing method of the leather-like sheet-like thing which consists of two types of solution of a polymeric elastic body (B), and apply | coats a polymeric elastic body (B2) after apply | coating drying to a sheet-like object. The method of claim 21, A leather-like sheet-like article wherein the polymer elastomer (B2) is a silicone-modified polyurethane. The method of claim 14, The manufacturing method of the leather-like sheet-like thing which consists of two types of solution of a polymer elastic body (C), and apply | coats a polymer elastic body (C2) containing an adhesive after apply | coating and drying a polymeric elastic body (C1) to the top part of a processus | protrusion part. The method of claim 23, The manufacturing method of the leather-like sheet-like thing whose adhesive is liquid rubber or rosin resin. The method of claim 24, The manufacturing method of the leather-like sheet-like thing whose liquid rubber is synthetic liquid rubber of molecular weight 800-5000. The leather-like sheet-like object of Claim 1 was stuck to the surface of the ball | bowl body, The ball characterized by the above-mentioned.